US6201047B1 - Method of stabilizing EPDM modified polypropylene by adding piperidine compounds - Google Patents
Method of stabilizing EPDM modified polypropylene by adding piperidine compounds Download PDFInfo
- Publication number
- US6201047B1 US6201047B1 US09/011,932 US1193298A US6201047B1 US 6201047 B1 US6201047 B1 US 6201047B1 US 1193298 A US1193298 A US 1193298A US 6201047 B1 US6201047 B1 US 6201047B1
- Authority
- US
- United States
- Prior art keywords
- epdm
- modified polypropylene
- formula
- stabilizing
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 45
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 40
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 40
- 150000003053 piperidines Chemical class 0.000 title claims abstract description 7
- 230000000087 stabilizing effect Effects 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims 11
- 229920002943 EPDM rubber Polymers 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000006096 absorbing agent Substances 0.000 claims abstract description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 238000010276 construction Methods 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 125000002950 monocyclic group Chemical group 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 abstract description 3
- 230000035939 shock Effects 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 description 17
- 230000006641 stabilisation Effects 0.000 description 15
- 238000011105 stabilization Methods 0.000 description 15
- 239000004611 light stabiliser Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- RSWPRDAJUOWGOE-DHZHZOJOSA-N C/C=C/C(=O)CC1CC(C)(CC)N(C)C(C)(CC)C1C Chemical compound C/C=C/C(=O)CC1CC(C)(CC)N(C)C(C)(CC)C1C RSWPRDAJUOWGOE-DHZHZOJOSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- KSCTZLAUFVYTDZ-UHFFFAOYSA-N CC1=CC=C(C=CC(=O)OC2CC(C)(C)N(C)C(C)(C)C2)C=C1 Chemical compound CC1=CC=C(C=CC(=O)OC2CC(C)(C)N(C)C(C)(C)C2)C=C1 KSCTZLAUFVYTDZ-UHFFFAOYSA-N 0.000 description 2
- UAYMRRZWJPKGLS-UHFFFAOYSA-N CN1C(C)(C)CC(OC(=O)C=CC2=CC=C(C=CC(=O)OC3CC(C)(C)N(C)C(C)(C)C3)C=C2)CC1(C)C Chemical compound CN1C(C)(C)CC(OC(=O)C=CC2=CC=C(C=CC(=O)OC3CC(C)(C)N(C)C(C)(C)C3)C=C2)CC1(C)C UAYMRRZWJPKGLS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920011250 Polypropylene Block Copolymer Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWHNXXMYEICZAT-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidin-4-ol Chemical compound CN1C(C)(C)CC(O)CC1(C)C NWHNXXMYEICZAT-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical class OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 description 1
- PHBCDAHASFSLMJ-UHFFFAOYSA-N 2-hydroxybenzotriazole Chemical class C1=CC=CC2=NN(O)N=C21 PHBCDAHASFSLMJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 0 CC1(C)N(*)C(C)(C)C(*)C(**C=CC)C1 Chemical compound CC1(C)N(*)C(C)(C)C(*)C(**C=CC)C1 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N CCCCCCCCOC1=CC=C(C(=O)C2=CC=CC=C2)C(O)=C1 Chemical compound CCCCCCCCOC1=CC=C(C(=O)C2=CC=CC=C2)C(O)=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- FYWXOBQIDYUWJS-FMIVXFBMSA-N COC1=CC=C(/C=C/C(=O)OC2CC(C)(C)N(C)C(C)(C)C2)C=C1 Chemical compound COC1=CC=C(/C=C/C(=O)OC2CC(C)(C)N(C)C(C)(C)C2)C=C1 FYWXOBQIDYUWJS-FMIVXFBMSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- IDMPFPPACDAAGR-UHFFFAOYSA-N OC(=O)C1=C(O)C=CC=C1C1(C(=O)C=2C(=CC=CC=2)O)C=CC=C(C(=O)C=2C(=CC=CC=2)O)C1 Chemical class OC(=O)C1=C(O)C=CC=C1C1(C(=O)C=2C(=CC=CC=2)O)C=CC=C(C(=O)C=2C(=CC=CC=2)O)C1 IDMPFPPACDAAGR-UHFFFAOYSA-N 0.000 description 1
- DDVCHWKTHJXBNU-UHFFFAOYSA-N OC1CCCCC1.[HH] Chemical compound OC1CCCCC1.[HH] DDVCHWKTHJXBNU-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- BZEQEORXAROPAN-UHFFFAOYSA-N [H]CC1CC(C)(CC)N(C)C(C)(CC)C1C Chemical compound [H]CC1CC(C)(CC)N(C)C(C)(CC)C1C BZEQEORXAROPAN-UHFFFAOYSA-N 0.000 description 1
- RJFHBGLPPVXLJY-UHFFFAOYSA-N [H]N(C)C1=NC(C)=NC(N(CCCCCCN(C)C2CC(C)(C)N([H])C(C)(C)C2)C2CC(C)(C)N([H])C(C)(C)C2)=N1 Chemical compound [H]N(C)C1=NC(C)=NC(N(CCCCCCN(C)C2CC(C)(C)N([H])C(C)(C)C2)C2CC(C)(C)N([H])C(C)(C)C2)=N1 RJFHBGLPPVXLJY-UHFFFAOYSA-N 0.000 description 1
- UWPZCEGCMHIAQG-UHFFFAOYSA-N [H]NC1C(C)(C)CC(OC(=O)CCCCCCCCC(=O)OC2CC(C)(C)C(N[H])C(C)(C)C2)CC1(C)C Chemical compound [H]NC1C(C)(C)CC(OC(=O)CCCCCCCCC(=O)OC2CC(C)(C)C(N[H])C(C)(C)C2)CC1(C)C UWPZCEGCMHIAQG-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011326 mechanical measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical class C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/40—Oxygen atoms
- C07D211/44—Oxygen atoms attached in position 4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Ethene-propene or ethene-propene-diene copolymers
Definitions
- the invention relates to the subject-matter of the Patent claims.
- the light stabilization of mouldings of EPDM-modified polypropylene in automotive construction, especially of car bumpers, is a particularly demanding task owing to the heterogeneous composition of the polymer matrix and its partial crystallinity, since (a) the migration of the light stabilizer to the surface must be prevented and (b) the light stabilization must be secured at a high level with good permanence over a long period of time.
- the object of the present invention was to stabilize EPDM-modified polypropylene, which is used in particular in automotive construction, against the effect of light.
- R 1 is hydrogen, hydroxyl, lower alkyl, lower alkoxy, acyl or oxygen
- R 2 is a substituted or unsubstituted, mono- or bicyclic radical of aromatic type
- R 3 is oxygen, —NH— or —N(C 1-4 -alkyl)- and
- R 8 independently at each occurrence is hydrogen or methyl
- EPDM-modified polypropylene which is employed in particular in automotive construction, such as for shock absorbers, cover strips and the like.
- lower alkyl are meant preferably radicals having 1-8, especially 1 or 2, carbon atoms; suitable acyl radicals are preferably those of formic, acetic or propionic acid.
- R 1 are preferably hydrogen, hydroxyl, methyl or C 1-8 -alkoxy, especially hydrogen or methyl, in particular methyl.
- R 2 of aromatic type examples include benzene, naphthalene and nitrogen- and/or sulphur-containing five- or six-membered rings with or without a fused-on benzene ring which carry, for example, sterically hindered hydroxyl as substituents (3,5-di-tert-butyl-4-hydroxyphenyl), or a thienyl radical.
- Aromatic six-membered rings are preferred. Examples of possible substituents on these rings are hydroxyl, lower alkyl or alkoxy, preferably methyl, tert-butyl, methoxy, ethoxy, hydroxyl and one or two further groups of the formula
- Every R 8 is preferably hydrogen.
- Additional stabilizers which can be employed for the EPDM-modified polypropylene include antioxidants, for example sterically hindered phenols, secondary aromatic amines or thioethers (described, for example, in “Plastics Additives”, Gachter and Muller, 1985, pp. 8-12), further HALS compounds, antistatic agents, flame retardants, plasticizers, nucleating agents, metal passivators, biocides and the like.
- the invention also provides for the combination of piperidine compounds of the formula I with known UV absorbers (2-(2′-hydroxyphenyl)benzotriazole compounds, 2-hydroxybenzotriazole compounds, 1,3-bis(2′-hydroxy-benzoyl)benzenesalicylates, cinnamic acid derivatives, triazine derivatives and oxalanilides). It has been found that by mixtures of compounds of the formula I and UV absorbers in a ratio of from 10:1 to 1:10, preferably from 4:1 to 1:4, depending on the thickness of the article to be stabilized, the equilibrium between diffusion rate and photochemical binding of stabilizers of the formula I to the polymer matrix can be influenced and thus the light stabilization effect improved.
- the HALS compounds in the interior of the mouldings that is, the piperidine compounds or piperidine radicals which act as stabilizer
- the piperidine compounds or piperidine radicals which act as stabilizer will diffuse slowly towards the surfaces where they are bound chemically to the EPDM-modified polypropylene as a result of the exposure which occurs in the course of service.
- any destroyed HALS stabilizers at the surface are continually replaced and stabilization is extended for a substantially longer time.
- Polymer articles which have been stabilized in accordance with the present invention against the damaging effect of UV light have the feature, not found in the prior art, that after only a short period of service and thus of exposure to light it is no longer possible to remove the stabilizers (compounds of the formula I) from the EPDM-modified polypropylene by physical means, even by eluting with solvents.
- the leaching i.e. the loss of stabilizers
- the polymers UV-stabilized in accordance with the invention exhibit a high resistance.
- EPDM-modified polypropylene with a basic level of stabilization is employed as the base material and is UV-stabilized in accordance with the invention in a second processing step.
- Basic stabilization is generally carried out, as is known, with 0.05-0.2% of a phenolic antioxidant and 0.05-0.5% of calcium stearate, based on the weight of the EPDM-modified polypropylene.
- the fault criterion is the bending test of injection moulded sheets following storage in a convection oven, i.e. the fracture of the sample on assessment.
- test sheets impact strength in accordance with DIN 53453
- the injection moulded sheets and test rods were produced with an injection moulding machine of the type Ahrburg IM at a temperature of 220-230°, 80 revolutions per minute, an injection pressure of 100 bar and a closing force of 12 kN.
- Injection moulded test sheets 2 mm thick produced from the basically stabilized EPDM-modified polypropylene from Example 2, to which the following compounds have been added in addition as light stabilizers, were subjected to artificial weathering.
- Example 1 Ab 5000 ppm of Sanduvor ® 2500 h 3944* *Sanduvor ® 3944 is a light stabilizer having a mean molecular weight of >2500 and a melting range of 100-135° from Clariant, of the formula
- Example Light stabilizer Failure after Ba 4500 ppm of compound from 30 days Example 1 Bb 5000 ppm Sanduvor ® 3944 14 days Bc 3000 ppm Tinuvin ® 770* 14 days 2000 ppm Sanduvor ® 3944 Bd 6000 ppm Tinuvin ® 770 7 days *Tinuvin ® 770 is a light stabilizer from Ciba-Geigy, of the formula
- the concentration ranges chosen for Uv absorbers in the above example take account of the known fact that UV absorbers, owing to their markedly lower activity as light stabilizers in comparison with HALS compounds, must be employed in approximately twice the concentration in the polymer in order to obtain approximately comparable light stabilizing effects in relatively thick articles as described in the present example (see Example De as against Da and Dd).
- the examples Db (50% HALS, 50% UVA) and Dc (20% HALS, 80% UVA) emphasize the outstanding activity of combinations of novel light stabilizers of the HALS type with UV absorbers, which is clearly expressed in the very small changes in mechanical properties after exposure, i.e. in the efficient UV stabilization of the polymer.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Hydrogenated Pyridines (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Graft Or Block Polymers (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19530468A DE19530468A1 (de) | 1995-08-18 | 1995-08-18 | Verwendung von Piperidinverbindungen |
| DE19530468 | 1995-08-18 | ||
| PCT/EP1996/003622 WO1997007159A1 (de) | 1995-08-18 | 1996-08-16 | Verwendung von piperidinverbindungen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US6201047B1 true US6201047B1 (en) | 2001-03-13 |
Family
ID=7769842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/011,932 Expired - Fee Related US6201047B1 (en) | 1995-08-18 | 1996-08-16 | Method of stabilizing EPDM modified polypropylene by adding piperidine compounds |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US6201047B1 (cs) |
| EP (1) | EP0845013B1 (cs) |
| JP (1) | JPH0959459A (cs) |
| KR (1) | KR19990037674A (cs) |
| AT (1) | ATE207510T1 (cs) |
| AU (1) | AU718364B2 (cs) |
| BR (1) | BR9609929A (cs) |
| CZ (1) | CZ46498A3 (cs) |
| DE (2) | DE19530468A1 (cs) |
| ES (1) | ES2165995T3 (cs) |
| HU (1) | HUP9802455A3 (cs) |
| MX (1) | MX9801268A (cs) |
| SK (1) | SK20498A3 (cs) |
| WO (1) | WO1997007159A1 (cs) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020156165A1 (en) * | 2000-10-10 | 2002-10-24 | Clariant International Ltd. | Polyolefin articles with long-term elevated temperature stability |
| US6486238B1 (en) * | 1998-12-21 | 2002-11-26 | Toyo Boseki Kabushiki Kaisha | Hindered amine compound, resin composition, polyurethane fiber and production method and use thereof |
| US20100036027A1 (en) * | 2007-01-04 | 2010-02-11 | Polyone Corporation | Thermally stable thermoplastic vulcanizate compounds |
| CN110117248A (zh) * | 2019-06-28 | 2019-08-13 | 烟台新特路新材料科技有限公司 | 一种受阻胺类紫外线吸收剂的制备方法 |
| CN110117249A (zh) * | 2019-06-28 | 2019-08-13 | 烟台新特路新材料科技有限公司 | 一种苯亚甲基受阻胺光稳定剂的制备方法 |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0952975A (ja) * | 1995-08-18 | 1997-02-25 | Clariant Internatl Ltd | 顔料の安定化方法及びこの方法に用いる組成物 |
| GB9607565D0 (en) * | 1996-04-12 | 1996-06-12 | Clariant Int Ltd | Stabilizer composition |
| EP0892828B1 (en) * | 1996-04-12 | 2001-05-30 | Clariant Finance (BVI) Limited | Stabilization of polyolefins |
| DE19618197A1 (de) * | 1996-05-07 | 1997-11-13 | Hoechst Ag | Neue sterisch gehinderte Piperidinderivate als Lichtschutzmittel für Polymere |
| WO2003096991A2 (en) | 2002-05-17 | 2003-11-27 | Othera Pharmaceuticals, Inc. | Amelioration of the development of cataracts and other opthalmic diseases |
| US7825134B2 (en) | 2003-05-19 | 2010-11-02 | Othera Holding, Inc. | Amelioration of cataracts, macular degeneration and other ophthalmic diseases |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3412227A1 (de) * | 1983-04-11 | 1984-10-11 | Sandoz-Patent-GmbH, 7850 Lörrach | Neue piperidinverbindungen |
| US5021478A (en) * | 1989-03-21 | 1991-06-04 | Ciba-Geigy Corporation | Compounds containing both UV-absorber and 1-hydrocarbyloxy hindered amine moieties and stabilized compositions |
| US5705545A (en) * | 1992-08-17 | 1998-01-06 | Clariant Finance (Bvi) Limited | Use of HALS compounds |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58113236A (ja) * | 1981-12-28 | 1983-07-06 | Tounen Sekiyu Kagaku Kk | ポリオレフイン組成物 |
| JPS63122752A (ja) * | 1986-11-12 | 1988-05-26 | Mitsui Toatsu Chem Inc | 塗装バンパ−用ポリプロピレン系樹脂組成物 |
| DE69008405T2 (de) * | 1989-03-21 | 1994-08-25 | Ciba Geigy Ag | Verbindungen mit sowohl UV absorbierenden als auch eine gehinderte 1-Hydrocarbyloxy-Aminogruppe enthaltenden Resten und damit stabilisierte Mischungen. |
| EP0437096B1 (en) * | 1989-12-27 | 1996-09-18 | Ube Industries, Ltd. | Polypropylene resin composition having improved coating property |
| JPH0952975A (ja) * | 1995-08-18 | 1997-02-25 | Clariant Internatl Ltd | 顔料の安定化方法及びこの方法に用いる組成物 |
-
1995
- 1995-08-18 DE DE19530468A patent/DE19530468A1/de not_active Withdrawn
-
1996
- 1996-03-29 JP JP8077056A patent/JPH0959459A/ja active Pending
- 1996-08-16 HU HU9802455A patent/HUP9802455A3/hu unknown
- 1996-08-16 MX MX9801268A patent/MX9801268A/es not_active IP Right Cessation
- 1996-08-16 BR BR9609929A patent/BR9609929A/pt not_active Application Discontinuation
- 1996-08-16 CZ CZ98464A patent/CZ46498A3/cs unknown
- 1996-08-16 AT AT96928472T patent/ATE207510T1/de not_active IP Right Cessation
- 1996-08-16 EP EP96928472A patent/EP0845013B1/de not_active Expired - Lifetime
- 1996-08-16 ES ES96928472T patent/ES2165995T3/es not_active Expired - Lifetime
- 1996-08-16 DE DE59608022T patent/DE59608022D1/de not_active Expired - Fee Related
- 1996-08-16 SK SK204-98A patent/SK20498A3/sk unknown
- 1996-08-16 US US09/011,932 patent/US6201047B1/en not_active Expired - Fee Related
- 1996-08-16 AU AU68222/96A patent/AU718364B2/en not_active Ceased
- 1996-08-16 KR KR1019980701153A patent/KR19990037674A/ko not_active Ceased
- 1996-08-16 WO PCT/EP1996/003622 patent/WO1997007159A1/de not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3412227A1 (de) * | 1983-04-11 | 1984-10-11 | Sandoz-Patent-GmbH, 7850 Lörrach | Neue piperidinverbindungen |
| US5021478A (en) * | 1989-03-21 | 1991-06-04 | Ciba-Geigy Corporation | Compounds containing both UV-absorber and 1-hydrocarbyloxy hindered amine moieties and stabilized compositions |
| US5705545A (en) * | 1992-08-17 | 1998-01-06 | Clariant Finance (Bvi) Limited | Use of HALS compounds |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6486238B1 (en) * | 1998-12-21 | 2002-11-26 | Toyo Boseki Kabushiki Kaisha | Hindered amine compound, resin composition, polyurethane fiber and production method and use thereof |
| US20020156165A1 (en) * | 2000-10-10 | 2002-10-24 | Clariant International Ltd. | Polyolefin articles with long-term elevated temperature stability |
| US6538056B1 (en) | 2000-10-10 | 2003-03-25 | Clariant International Ltd. | Polyolefin articles with long-term elevated temperature stability |
| US6774170B2 (en) | 2000-10-10 | 2004-08-10 | Clariant Finance (Bvi) Limited | Polyolefin articles with long-term elevated temperature stability |
| US20100036027A1 (en) * | 2007-01-04 | 2010-02-11 | Polyone Corporation | Thermally stable thermoplastic vulcanizate compounds |
| EP2097474A4 (en) * | 2007-01-04 | 2010-10-06 | Polyone Corp | HEAT-RESISTANT THERMOPLASTIC VULCANATE COMPOUNDS |
| CN110117248A (zh) * | 2019-06-28 | 2019-08-13 | 烟台新特路新材料科技有限公司 | 一种受阻胺类紫外线吸收剂的制备方法 |
| CN110117249A (zh) * | 2019-06-28 | 2019-08-13 | 烟台新特路新材料科技有限公司 | 一种苯亚甲基受阻胺光稳定剂的制备方法 |
| CN110117248B (zh) * | 2019-06-28 | 2022-05-31 | 烟台新特路新材料科技有限公司 | 一种受阻胺类紫外线吸收剂的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CZ46498A3 (cs) | 1998-06-17 |
| ATE207510T1 (de) | 2001-11-15 |
| JPH0959459A (ja) | 1997-03-04 |
| WO1997007159A1 (de) | 1997-02-27 |
| EP0845013A1 (de) | 1998-06-03 |
| EP0845013B1 (de) | 2001-10-24 |
| AU718364B2 (en) | 2000-04-13 |
| SK20498A3 (en) | 1998-09-09 |
| DE59608022D1 (de) | 2001-11-29 |
| HUP9802455A3 (en) | 1999-04-28 |
| AU6822296A (en) | 1997-03-12 |
| BR9609929A (pt) | 1999-07-06 |
| MX9801268A (es) | 1998-05-31 |
| HUP9802455A2 (hu) | 1999-03-29 |
| ES2165995T3 (es) | 2002-04-01 |
| DE19530468A1 (de) | 1997-02-20 |
| KR19990037674A (ko) | 1999-05-25 |
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Legal Events
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| AS | Assignment |
Owner name: CLARIANT FINANCE (BVI) LIMITED, VIRGIN ISLANDS, BR Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:AVAR, LAJOS;LIGNER, GILBERT;THUERMER, ANDREAS;REEL/FRAME:011505/0591;SIGNING DATES FROM 19980107 TO 19980112 |
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| STCH | Information on status: patent discontinuation |
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